Sulfolanyl alkyl ethers in dyeing cellulose acetate, polyvinylidine cyanide and glycol-dicarboxylic acid polymer filaments



United States Patent SULFOLANYL ALKYL ETHERS IN DYEING CEL- LULOSEACETATE, POLYVINYLIDINE CYANIDE AND GLYCOL-DICARBOXYLIC ACll) POLYMERFEAMENTS Martin Kallman and Victor Salvin, Charlotte, N.C., as-

signors to Celanese Corporation of America, New York, N.Y., acorporation of Delaware No Drawing. Filed Apr. 5, 1961, Ser. No. 160,798

4 Claims. (Cl. 855) The present invention relates to novel processes fordyeing synthetic filamentary materials and particularly to processes fordyeing selected synthetic filamentary materials with disperse dyes. 1

Disperse dyes were developed for the dyeing of secondary celluloseacetate, being applied from aqueous dispersion usually at elevatedtemperature. Take up of dye by the filamentary material is slow andincomplete. Where another filamentary material such as cotton or wool.is present it is often stained, but not dyed, by the disperse dyeespecially where dyeing is carried out ,over prolonged periods withheat. Substances, called accelerants, have been found which 'willaccelerate the take up of dye by the fiber and also increase theexhaustion. The reduced dyeing time minimizes the time during which ablend fiber is exposed to the dye and thus may diminish staining. On the.other hand the accelerant may promote staining of the blend fiber andwhether or not staining will occur is incapable of prediction, dependingupon dyeing time, depth of shade, dyeing temperature, etc. In addition,certain accelerants by virtue of their volatility are of utility onlywhen dyeing at w temperatures or under pressure.

The choice of an accelerant for a new filamentary material or the choiceof a new accelerant for an old filamentary material is difficult sinceaccelerants for one filamentary material may not function satisfactorilyon another. Moreover, prediction is rendered impossible because theexact mechanism by which an accelerant functions is not understood.While it has been postulated that the accelerant swells the filamentarymaterial to be dyed numerous known swelling agents are unsuited asaccelerants either because they fail to speed up dyeing, because theycause staining of blend fibers, because they damage the principal orblend fiber, etc.

It is accordingly an object of the present invention to provideaccelerants for dyeing nytril, polyester, cellulose triacetate andsecondary cellulose acetate filamentary materials with disperse dyes.

A further object of the invention is to provide accelerant dyeingprocesses for dyeing blends of the aforementioned filamentary materialswith other filamentary materials.

Other objects and advantages of the invention will become apparent fromthe following detailed description and claims wherein all parts are byweight unless otherwise specified.

In accordance with one aspect of the present invention dyeing of afilamentary material selected from the group consisting of nytril,polyester, cellulose triacetate and secondary cellulose acetatefilamentary materials is carried out with a dispersion in water of adisperse dye and a non-volatile accelerant selected from the groupconsisting of an alkyl sulfolanyl ether and a substituted alkylbenzoate, the dyebath being applied by immersion, spraying, padding,etc. The accelerants boil in excess of about 175 C. and thus are suitedfor dyeing without pressure at high temperatures in excess of about 95C., although lower temperatures may also be employed.

Representative sulfolanyl ethers which may be employed in accordancewith the invention include the ethers of 3-sulfolanyl alcohol with analkanol preferably containing about four to ten carbon atoms, e.g.,butyl 3- .tsulfolanyl ether, isooctyl 3-sulfolanyl ether,hydroxyethoxyethyl 3-sulfolanyl ether, ethoxypropyl 3-sulfolanyl ether,and the like. Ethers of substituted sulfolanyl alcohols and sulfolanylalcohols with the hydroxyl group in 2-position can also be used.

Advantageously the substituted alkyl benzoates which may be employed inaccordance with the invention have a total of about 9 to 12 carbon atomsand preferably the substituents are lower alkyl or lower alkoxy radicalsattached either to the benzene ring or to the alkyl ester group, e.g.,methyl p-tolua-te, methoxyethyl p-toluate, methoxyethyl benzoate, andthe like.

The accelerants are generally employed in about 2 to 20% and preferablyabout 5 to 12% on the weight of fiber. dyeing sufficiently and largeramounts are uneconomical. The concentration of accelerant in the dyebathmay vary within wide limits, e.g., as low as about 0.1% Whenwinch dyeingor as high as about 6% when jig dyeing although even higher orlower'concentrations can be tolerated. Advantageously there is alsopresent in the dyebath about 0.02 to 0.2 and preferably about 0.04 to0.1% of an emulsifying agent, e.g., an anionic agent such as sodiumdodecylbenzene sulfonate or'a nonionic agent such as an alkarylpolyetheralcohol. This serves to maintain in dispersed condition the accelerantwhen the latter is present in excess of its solubility and it alsomaintains in dispersion the dyestuti which is generally present in about1 to 10% on fabric weight depending upon its color and the desiredshade. Other ingredients conventional in the dyeing art such asthickeners, humectants, or the like can also be present in the dyebathespecially when printing. The temperature and duration of dyeing willdepend upon each other as well as upon the identity of the filamentarymaterial, the dye and the accelerant and upon the depth of shadedesired. Generally, the temperature of the dyebath ranges between about50 C. and the boil and most frequently between about C. and C. Pressureequipment will permit use of temperatures above the normal boiling pointof the dyebath and will permit a particular effect to be achieved with asmaller proportion of accelerant.

In accordance with another aspect of the invention it has been foundthat the use of p-methyl toluate as an accelerant for dyeing nytrilfilamentary material is particularly eificacious resulting in fullshades, high exhaustion and rapid dyeing. Other accelerants heretoforeemployed with other fibers 'do not yield equally satisfactory results.

The recited filamentary materials may be dyed in blends with one anotherin which event more or less uniform coloration, i.e., union dyeing, willbe achieved. The recited filamentary materials may also be dyed inblends with other filamentary materials to which disperse dyes arenon-substantive such as wool, cotton, rayon, or the like, in which eventa reserve effect will be achieved. It is an advantage of the presentinvention that little or no staining of such other filamentary materialoccurs and whatever slight staining occurs can readily be cleared. It isalso possible to include in the dyebath dyes substantive to the otherfilamentary materials so as to obtain a cross-dyed effect.

The filamentary materials dyed in accordance with the invention may bein the form of garments or other finished articles, knit, woven ornon-woven fabrics, filament or spun yarn, tow, roving, sliver, staplefiber, or the like.

As employed herein, nytril refers to filamentary materials comprisingpolymers of vinylidene cyanide. These may be homopolymers oradvantageously copolymers with one or more monomers such as vinylacetate, styrene, or the like. A preferred material is a copolymercomprising about 45 to 55 mol percent of vinylidene cyanide, e.g.,

Patented Nov. 10, 1964 Smaller amounts generally do not accelerate.

the vinylidene cyanide and vinyl acetate form a copolymer in which thedilferent monomer units are alternated in regular manner as in theproduct sold under the trademark Darvan. Polyester refers to linearsuperpolyesters such as the condensation products of ethylene glycol,polyethylene glycol and/or another glycol with terephthalic acid and/orother dicarboxylic acids such as adipic or sebacic acid, e.g.,polyethylene terephthalate, such as is sold under the trademark Fortrel.

Cellulose triacetate refers to cellulose acetate having an acetyl valuein excess of about 59% and preferably in excess of about 61%. Secondarycellulose acetate has reference to acetone soluble cellulose acetate,i.e., cellulose acetate having an acetyl value of about 54 to 58% byWeight calculated as combined acetic acid.

The filamentary materials may contain other chemical entities either inthe polymer chain or as additives cospun therewith or subsequentlyapplied for the purpose of varying the physical and/or chemicalproperties such as dye receptivity.

The invention will be further described in the following illustrativeexamples.

Example I (a) 10 parts by weight of 3 denier staple fibers of acopolymer comprising alternating units of vinylidene cyanide and vinylacetate (sold under the trademark Darvan) are immersed in 300 parts ofwater at 50 C. and containing 1.2 parts of methyl p-toluate and 0.3 partof sodium dodecylbenzenesulfonate. After 10 minutes of agitation, 0.3part of the disperse dye l-methylamino 4,B-hydroxyethylaminoanthraquinone (Disperse Blue 3) is added, the bathtemperature is raised to 95 C. over 30 minutes. After two hours ofagitation, the bath is dropped, the fiber is rinsed for 5 minutes incold running water, scoured for 20 minutes at 80 C. with a 0.1% soapsolution, rinsed again in cold running water and dried. The dyed fabricis fast to light as well as to washing and dry cleaning solvents,indicating that the dye is in the fiber and not just held on thesurface. The shade is full, the dye being approximately 65% exhaustedfrom the bath.

([2) A control run, identical except for omission of the methylp-toluate, resulted in a pastel shade and only about exhaustion of thedye from the bath.

(0) Substituting o-phenylphenol for the methyl ptoluate, the color valueand dye exhaustion are almost 20% less than (a).

Example 11 The process of Example I is repeated except that the fiber iscellulose triacetate having an acetyl value of 61.9%. The fiber is dyeda full shade with 70% exhaustion of the dyebath. Without accelerant only40% exhaustion is obtained.

Example III The process of Example I is repeated on fibers ofpolyethylene terephthalate. 60% exhaustion of the dyebath is acchievedcompared with only 10% in the absence of accelerant.

Example IV The process of Example I is repeated except that the methylp-toluate and the sodium dodecylbenzenesulfonate are respectivelyreplaced by isoctyl 3-sulfolanyl ether and an alkylarylpolyether alcoholsold under the trademark Triton X102. Substantially the same results areachieved as in Example I.

4. Example V The process of Example IV is repeated except that the fiberis cellulose triacetate having an acetyl value of 61.9% and the dye is aprototype of Disperse Blue 27.

Example VI The process of Example V is repeated employing Disperse Red35 as the dye and replacing the fiber by 10 parts of a check fabricwoven of alternate warp and filling bands of wool and of cellulosetriacetate having an acetyl value of 61.9%. The cellulose triacetate isdyed a deep shade and the wool is stained so slightly that it could bedyed even without a pre-scour; as a matter of fact a wool dye could beincorporated into the same dyebath since it is not necessary to removestain from the Wool. The relative absence of stain permits the wool tobe dyed lighter shades and it renders the dyeing more washfast and lightfast since if the wool had picked up disperse dye'it would give it upwhen not desired. In addition the absence of wool stain makes it easierto match shades.

As contrasted with o-phenylphenol or other carriers heretofore employedthe depth of shade on the cellulose triacetate is greater and the Woolstaining is appreciably less while the exhaustion is at least equal.

It is to be understood that the foregoing detailed description is givenmerely by way of illustration and that many variations may be madetherein without departing from the spirit of our invention.

Having described our invention what We desire to secure by LettersPatent is:

1. The process which comprises immersing a filamentary material selectedfrom the group consisting of vinylidine cyanide polymer, polyestercondensation prodact of a glycol and a dicarboxylic acid, cellulosetriacetate and secondary cellulose acetate filamentary materials in anaqueous dispersion of a disperse dye containing about 0.1 to 6% of analkyl sulfolanyl ether present in an amount ranging from about 2 to 20%of the weight of said filamentary material.

2. The process set forth in claim 1, wherein said alkyl sulfolanyl etheris the ether of 3-sulfolanyl alcohol with an alkanol having about fourto ten carbon atoms.

3. The process which comprises immersing a filamentary material of apolyester condensation product of a glycol and a dicarboxylic acid, inan aqueous dispersion of a disperse dye containing about 0.1 to 6% ofthe ether of sulfolanyl alcohol with an alkanol having about four to tencarbon atoms, said ether being present in about 2 to 20% of the Weightof said filamentary material.

4. The process which comprises immersing a cellulose triacetatefilamentary material in an aqueous dispersion of a disperse dyecontaining about 0.1 to 6% of the ether of sulfolanyl alcohol with analkanol having about four to ten carbon atoms, said ether being presentin about 2 to 20% of the weight of said filamentary material.

References Cited in the file of this patent UNITED STATES PATENTS OTHERREFERENCES Chem. Abstracts, 1959, page 1850.

1. THE PROCESS WHICH COMPRISES IMMERSING A FILAMENTARY MATERIAL SELECTEDFROM THE GROUP CONSISTING OF VINYLIDINE CYANIDE POLYMER, POLYESTERCONDENSATION PRODUCT OF A GLYCOL AND A DICARBOXYLIC ACID, CELLULOSETRIACETATE AND SECONDARY CELLULLOSE ACETATE FILAMENTARY MATERIALS IN ANAQUEOUS DISPERSION OF A DISPERSE DYE CONTAINING ABOUT 0.1 TO 6% OF ANALKYL SULFOLANYL ETHER PRESENT IN AN AMOUNT RANGING FROM ABOUT 2 TO 20%OF THE WEIGHT OF SAID FILAMENTARY MATERIAL.